Regenerating contact material



Dec' ll. 1945' CTE. HEMMINGER REGENERATING CONTACT MATERIAL 5 Sheets-Sheet 1 Original Filed April l, 1959 Ffa -J cAs ouv-ET I Pula l/v G GA s naar Cien elf/vc cfm MBE' CAS INLET \\.l\lll\l\ll\\ll\ll. illlnl... illlllllllllll llllllllllllllllllllll l llllll It M l i @aM/l Dec- 11 1945' i c. E. HEMMINGER REGENERATING CONTACT MATERIAL original Filed April 1, 19:59

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REGENERATTNG CONTACT MATERIAL 3 Sheets-Sheet 3 original Fi1ed Apri1 1, 1939 exa/ewa Patented Dec. 1l, 1945 REGENERATING CONTACT MATERIAL Charles E. Hemminger, Westfield, N. J., assigner to Standard Oil Development Company, a corporation of Delaware Original application April 1, 1939, Serial No. 265,388. Divided and this application yApril 19,

1943, Serial No. 483,602

22 Claims.

This invention relates to improvements in the continuous conversion of relatively heavy hydrocarbons into valuable hydrocarbon fractions such as those boiling within the gasoline range.

Th'e object of this invention is to provide a continuous catalytic process using such suitable apparatus including a catalyst conveying means as will enable efficient and economical treatment of hydrocarbons.

In carrying the invention into eiect, a catalyst conveying means, such as a Redler conveyor of the loop type, is employed to move the catalyst through a cracking or reaction zone. The conveyor lifts the catalysts against the oil vapors which flow generally downwardly but with' a stepwise to and fro transverse motion across the vertical column of rising catalyst, thus ailording a substantially right angular ow of oil vapors with respect to the moving catalyst. Furthermore, the oil vapors enter the cracking zone at a point where the catalyst is least effective, i. e. contains greatest amount of poisons or contaminants and cracked vapors leave the reaction zone at a -point about where fresh catalyst enters the reaction chamber. 'I'he catalyst which may be a solid siliceous material, a zeolite, coke, bauxite, clay or the like, is as indicated, during contact with heated hydrocarbon oil uid, poisoned or contaminated with a carbon containing material and consequently requires regular revivlcation after it has accumulated about 2% by weight or more of the poisons.

The poisoned catalyst leaving the cracking zone is discharged into an inclined chute or casing where it may be purged to drive off volatile hydrocarbons and then passes downwardly by Vgravity through a regeneration chamber comprising a plurality of vertical ducts disposed between baied fiues. A hot combustion supporting gas ows generally upwardly but also laterally to and l chamber interior showing the arrangement of catalyst ducts, ues, bailies and cooling tubes; and

Fig. 4 is a fragmentary perspective view of the tail portion of the conveyor.

Referring to Figs. 1 to 4 and speaking generally at first, the cracking apparatus comprises a cracking zone I, a catalyst purging chamber 2, a catalyst regeneration chamber 3, and a second purging and conditioning chamber 4. The cracking zone I consists of two elongated flues 5 carrying a plurality of baffles 6, constructed and arranged on opposite sides of conveyor 1. Referring at this point to Fig. 2 which shows an arfro through the down ilowing catalyst in a subf stantially right angular flow with respect to the catalyst. are perforated thus permitting the combustion SuppOl'tiIlg gas to flow into and out of the catalyst ducts. The result of the treatment of the poisoned catalyst with the combustion supportinggas is to burn off and/or oxidize the catalyst poisons or contaminants causing impairment of The walls forming the catalyst ducts i rangement of conveyor and flues coming within the purview of this invention, the flues 5 have the same depth as the casing of conveyor l, as shown. The Walls 8 of the conveyor 'I carry perforations 8a, thus permitting interilow of oil vapors between ilues 5 and conveyor 1 carrying catalyst C. In other words, ues 5 and the conveyor 'I have common walls 8 carrying perforations 8a which perforations may be about 5716" in diameter and may be spaced apart from center to center an inch or so.

The conveyor, as a whole comprises a tail portion T, a main portion M, a head portion H and a loop L (see Fig. 1) As may be seen from Figs. 2 and 4, the conveyor consists essentially of a casing or wall portion I0 having four walls and may be of steel or cast iron construction.` The conveying element consists of va plurality of detachable U-shaped iiights II spaced apart and connected by links I2.- (See Figs. 2 and 4).

The spent catalyst in cracking zone I is elevated by conveying nights II to the height of reservoir I4 into which it is discharged and the flights I I then pass over the sprockets |50 located Purging chamber 2 is formed by elevatable,.

gates I8 and I9 and the portion of casing I1 therebetween. Purging gas inlet 20 is in communication with valved conduit 2I leading into cracking zone I, as well as conduit 22 leading into purging chamber 2. It is seen from Fig. 1 that catalyst C may be admitted for purging by gravity ilow into chamber 2 by elevating gate I8. After the purging operation, gate I 3 is lowered until it divides or separates the catalyst in I4 from that in chamber 2, and then the gate I9 is elevated permitting ilo'w of catalyst into regeneration chamber 3. When all of the catalyst has been discharged from chamber 2, gate I9 is again lowered and another charge of catalyst is admitted to the chamber 2 from reservoir I4 for purging. Reservoir I4 should be suiciently large to permit continuous discharge of catalyst from conveyor 1- since, as explained, the operation of chamber 2 in purging is on intermittently moving catalyst.

The catalyst discharged from the chamber 2 falls by gravity through regeneration chamber 3 in ducts 22, the iiow being directed into said ducts 'by virtue of crown pieces or caps 23.. Each duct 22l is separated from the next duct by ilues 24 carrying baiiies 25 (see Fig. 3). The vertical walls forming the catalyst ducts 22 carrying perforations 36 throughout their length and breadth. These perforations may be about 1%" in diameter and spaced apart an inch o`r so, from center to center. Flues 24 carry banks of tubes 20 through which water or some other cooling uid may be circulated.

Referring now to Fig. 1, the regeneration chamresults can be obtained using lower pressures or considerably higher pressures. It is advisable. though not necessary to introduce direct steam into the cracking zone as through pipes 20 and 2|. This steam actually assists in the cracking reaction and further tends to counteract or prevent the tendency of oil vapors to ascend toward chamber I4. Furthermore, housing 55 of loop portion L of conveyor 1 is preferably filled with steam admitted through inlet 52 and withdrawn through.

53. This steam also forms a seal preventing the escape upwardly of oil vapors in the upper portions of i'lues 5. c

Since the oil cracking reaction is endothermic, it is desirable to dispose banks of tubes (not shown) in ilues 5 containing or flowing therethrough superheated steam and to cause the oil vapors to flow through said banks of tubes to compensate by heat transfer from the superheated steam for the heat lost during the cracking operation. The cracked vapors are withdrawn for fractionation through valved conduit 5I.

The column of catalyst proceeding upwardly is progressively contaminated by deposits resulting Vfrom the cracking operation until finally it becomes necessary to regenerate it. The length of the catalyst column lshould be such that too great an amount of deposit was not present on the catalyst before it was removed from the cracking chamber. That is to say, efficient operation may be achieved where the cracking zone is say to 50 feet long. Furthermore, a catalyst column cross-sectional area of 2 feet by 4 feet gives good results.

ber 3 is provided with a regeneration gas inlet 35 The poisoned catalyst which has been lifted 21, with recycle regeneration gas line 29 carrying i cycled are withdrawn from the system.

As indicated by the directional arrows in Figs. 1 and 3, the construction and arrangement of ilues and baiiles causes a generally upwardly, but also to and fro transverse flow of regeneration gas through the downcoming catalyst.

A receiving vessel 4 forms a temporary repository for catalyst regenerated in chamber 3. The receiving vessel is provided with purging gas inlet 40. The purged catalyst is returned to the tail section T of conveyor 1 through hopper I5.

In order to give a specic example illustrating the present invention in actual operation,` the following description is given with the explanation that the invention is not limited by the precise details of said specific example.

Heated hydrocarbon vapors from any conventional source are introduced in chamber I through valved conduit 50 near the top of the chamber. The hydrocarbon vapors may be a gas oil cut heated to a temperature of about 820 F. or thereabouts. The heated vapors in the upper portion of i'lues 5 are caused by baiiles 6 to flow laterally through the perforations 8a in the walls 8 of the conveyor casing into one side of the rising solid column of catalyst C and to flow out through the opposite perforated wall 8 into the opposite flue, thence reverse its direction and flow through the column of catalyst in the opposite direction, but at a lower level. into the opposite flue. This type of iiow continues through the whole length of` the column of catalyst until finally the cracked products are withdrawn through conduit 5I. The temperature of the catalyst Should be in the neighborhood of 800 F. to 830 F. and the pressure in the cracking zone should be about 5 lbs.

per square inch on the gauge, but, 0f course, good through the cracking zone is discharged into reservoir I4 and eventually ilows into purging chamber 2. The operation in chamber 2 is intermittent and since catalyst is continuously discharged 40 into I4, it is apparent that I4 must be of sufiivzes cient relative size with respect to chamber 2 to accommodate this situation.

Assuming chamber 2 is empty, the same is filled by lifting gate I8 `to the height shown in Fig. 1, while gate I9 is lowered. When the chamber 2 is filled, gate I8 may be lowered. A purging gas, such as superheated steam at a temperature of say between 700 F. and 830 F. is forced into chamber` 2 through-conduits 20 and 22 and withdrawn through exhaust line 60. Instead of using steam, flue gas, nitrogen, carbon dioxide ormixtures thereof may be used for purging.

Following purging, the catalyst is discharged into regeneration chamber 3 by raising gate I9. The catalyst falls through ducts 22 to a receiver 4. Meanwhile, air or some oxygencontaining gas is admitted through line 27 into the bottom of the regeneration chamber. This air or other regeneration gas may have an inlet temperature of about 700 F. and is caused to flow laterally through descending catalyst and also stepwise upwardly by the bailles 25 toward outlet pipe 28. The regeneration gas flows through the perforations 36 in the walls of the catalyst ducts from the ilues into the ducts and out again in a cross-wisev reversing flow. Arriving at about the region where the inlet pipe 29 is attached to the regeneration chamber, the air or other gas is admixed with recycle gas consisting largely of carbon dioxide and steam. The ad* mixture causes a reduction in the oxygen concentration of the regeneration gas to about 10% more or less.

At about midway between the point where'recycle gas enters chamber 3 andthe products 'of combustion are withdrawn, the oxygen concentration should be about whereas nea;- the top of the regeneration column, the oxygen concentration is about 2%. The advantage of this oxygen concentration gradient is that the most highly contaminated catalyst encounters a low oxygen concentration, while toward the end of the regeneration a high oxygen concentration, say or more, is encountered by the catalyst in removing the last traces of tar material or coke. The oxygen concentration of the regeneration may vary from 30% at the inlet to 10% at'the outlet. lt may be advisable to, in certain installations, provide two or more recycle gas inlets at various levels in regeneration chamber 2li to obtain the desired oxygen concentration gradient. It may also be advisable to provide ducts it with a number oi' steeply inclined bailes to cause the downcoming catalyst to describe a somewhat tortuous path.

The oxygen-containing gas or the pure air, as the case may be. causes, upon contact with the catalyst, combustion or oxidation or distillation of the poisons or contaminants of catalyst C during its passage `through chamber The temperature of the combustion reaction can be controlled by circulating a cooling :duid such as cold water through coils 2@ (see Fig. 3). Temperature indicating devices, such as thermocouples (not shown) should be disposed in the nues at several points through the length of the regeneration chamber and, based on such readings or indications, the temperature of the catalyst at any time during regeneration should be maintained below ll5ll F. in the cas-e oi' most catalysts.

The gas pressure prevailing in the regenerator should be between 5 pounds per square inch and 140 pounds per square inch with about it pounds per square inch preferred.

Finally, the regenerated catalyst, which has fallen to chamber i is again purged and conditioned by superheated steam or the like intro duced through valved conduit lil and thereafter immediately discharged into hopper it and thence directly into the tail oi the Rodier conveyor for relntroduction intothe cracking chamber i.

Numerous modifications may be made in the invention as above disclosed without departing from the spirit thereof. For example, the catalyst conveyor need not be a Rodier type, but might be a belt or bucket conveyor. The regeneration chamber may be square, rectangular or circular in cross section. Furthermore, a powdered, granular or lump catalyst may be employed. ln the case where a powdered catalyst is employed, the perforations in the casing of the conveyor andthe ue walls may require reduction in diameter from about IAG to /a of an inch. Various other modifications falling within the scope of the invention are permissible without departing from the spirit of the invention.

This case is filed as a division of my application Serial No. 265,388, illed April l, 1939, now U. S. Patent 2,317,379 for Catalytic cracking apparatus.

i claim:

l. The method of continuously regenerating spent contact material containing carbonaceous deposits thereon which method comprises continuously introducing/saidcontact material into a regeneration zone and continuously withdrawing contact material therefrom at such rates as to maintain a moving bed of contact material in said regeneration zone, continuously introducing air into said zone and continuously removing regeneration gas therefrom, maintaining o heat exchange zone adjacent the regeneration zone and substantially coextensive therewith, introducing a heat exchange medium into said heat exchange zone, withdrawing heated heat exchange medium from said heat exchange zone and transferring heat from contact material in all parts of said regeneration zone to said heat exchange zone by circulating a heat transfer medium throughout said regeneration zone and contacting said heat transfer medium with said heat exchange zone in the course of` its circulaspent Contact material containing carbonaceous deposits thereon, which method comprises passing said contact material through` a regeneration zone in a substantially vertical moving bed retained between perforated walls, continuously passing hot inert and regenerating gases through said moving bed in a direction generally transverse to the movement oi the contact material in said bed, adjusting the temperature of said gases prior to their lpassage through said bed and recycling at least a portion of.'said gases through said bed to control the temperature of the contact material during regeneration.

ll. The method of continuously regenerating spent contact material containing carbonaceous deposits thereon, which method comprises passing said contact material through a regeneration zone in a substantially vertical moving bed retained between perforated walls, continuously passing hot inert and regenerating gases through said moving bed in a direction generally transverse to the movement of the contact material in ysaid bed, adjusting the temperature of said gases prior to their passage through said bed and recycling said gases through said bed at such a rate to control the temperature of the regeneration reaction.

5. The method or continuously regenerating spent contact material containing carbonaceous deposits thereon, which method comprises passing said contact material through a regeneration zone in a substantially vertical moving bed retained between perforated walls, continuously passing regenerating gas through the moving bed in a direction generally transverse to the movement of the contact material in the bed, removing regeneration gas from the system, recycling at least a part of the removed regeneration gases through the bed and passing the recycled regenerationv gas over cooling tubes alongside of said perforated walls and adjacent the moving ,bed before introducing it into the bed to control the temperature during regeneration.

6. A method of regenerating solid contact materlal which has become contaminated with carbonaceous deposits, which comprises passing the contact material by gravity in a relatively thin moving bed through a regeneration zone, passing hot lnegenerating gases through said moving bed in a direction generally transverse to the ilo-w of ysaid bed, continuously recycling a portion of withdrawn regeneration gases through said bed, adjusting the temperature of said recycled gases to control the temperature of said moving bed, continuously introducing an active regeneration gas into the recycled gas stream and continuously 4 withdrawing spent regeneration gas from the system. 7. The method of continuously regenerating spent contact material containing carbonaceous deposits thereon, which method comprises passing said contact material through a regeneration zone in a substantially vertical moving bed retained between perforated walls, continuously passing regenerating oxygen-containing gas through the moving bed in a direction generally transverse to the movement of the contact material in the bed, removing regeneration gas from the system and recycling at least a portion of the removed regeneration gas to control the oxygen concentration of the regenerating gas being passed through said moving bed.

8. A method of regenerating solid contact material which has become contaminated with carbonaceous deposits, which `comprises passing the contact material by gravity in a relatively thin moving bed through a regeneration zone, introvducing oxygen-containing regenerating gas into the bottom portion of the bed whereby fresh rel terial which has become contaminated with carbonaceous deposits, which comprises passing the contact material by gravity in a relatively thin moving bed through a regeneration zone, passing hot regenerating gases back and forth through said moving bed in a direction generally transvverse to the flow of the bed, cooling the regenerating gases after they have passed through the bed and again passing at least a portion of the regenerating gases through the bed.

10. A method of regenerating solid contact material which has become contaminated with carbonaceous deposits, which comprises passing the contact material by gravity in a relatively thin moving bed through a regeneration zone, passing hot regenerating gases through said mov- -ing bed-in a direction generally transverse to the flow of the bed a plurality of times and cooling the regeneration gases after they have passed through the bed and before they are again passed through the bed.

11. A method of regenerating solid contact material which has become contaminated with carbona-ceous deposits, which comprises passing vthe contact material by gravity in a plurality of relatively thin beds moving through a regeneration zone, passing hot regenerating gas back and forth across each moving bed in a direction generally transverse Vto the flow of the beds and passing the regenerating gas over cooling tubes after it passes across each bed to control the temperature of the regenerating gas. e

12. A method according to claim 11 wherein a portion of the regenerating gas in admixture with active regenerating gas is recycled through at least one of the beds.

` 13. A method of regenerating solid contact material which has become contaminated with carbonaceous deposits, which comprises passing the contact material by' gravity in a relatively thin moving bed through a regeneration zone, passing an oxidizing gas through the moving bed in a direction generally across the bed, passing the oxidizing gas over cooling tubes alongside the moving bed and containing a heat exchange medium so that heat is absorbed from the oxidizing gas, passing the cooled oxidizing gas through the bed and again cooling the gas.

14. The method oi eiecting rapid regeneration of solid contact material which has become contaminated with carbonaceous deposits, which method comprises passing said contact material by gravity in a relatively thin moving bed through a regeneration zone, passing hoff; gases through said moving bed' in a direction generally transverse to the iiow of said bed, continuously recycling said gases through said bed, adjusting the temperature of said recycled gases to maintain a desired regeneration temperature in said moving bed, continuously introducing an active regeneration gas into the recycled gas stream and continuously withdrawing spent regeneration gas from the system.

15. The method of continuously regenerating spent contact material containing carbonaceous deposits thereon, which method comprises'passing said contact material through a regeneration zone in a substantially vertical moving bed retained between perforated walls, continuously passing hot inert and regenerating gases through said moving bed in a direction generally transverse to the movement of the contact material in said bed, adjusting the temperature of said gases prior to their passage through said bed and continuously recycling said gases through said bed a plurality of times to maintain the temperature of the contact material in the moving bed below a maximum temperature of about l F.

16. The method of continuously regenerating spent contact material containing carbonaceous deposits thereon, which method comprises passing said contact material through a regeneration zone in a substantially vertical moving bed retained between perforated walls, continuously passing hot inert and regenerating gases through said moving bed in a direction generally transverse to the movement of the contact material in said bed, adjusting the temperature of said gases prior to their passage through said bed and continuously recycling said gases through said bed to control the regeneration reaction and to maintain the temperature of the contact material below a maximum temperature.

17. The method of continuously regenerating spent contact material containing carbonaceous deposits thereon, which method comprises passing said contact material through a regeneration zone in a substantially vertical moving bed re.

tained between perforated walls, continuously passing hot inert and regenerating gases through said moving lbed in a direction generally transverse to the movement of the contact material in cycling said gases through said bed, adjusting the eration gas is first contacted with the lower portion of said moving bed and spent regeneration gas is withdrawn from an upper portion of said moving bed.

21. The method according to claim 14 wherein the recycled gas stream comprises at least part of the spent regeneration gas Withdrawn from the system.

`22. The method according to claim 'Z wherein the active regenerating gas containing oxygen is rst contacted with the lower portion of said moving bed and regeneration gas is removed from the upper portion of said moving bed.

CHARLES E. HEMMINGER.- 

